Process for the treatment of hydrocarbons



Oct. 9, 1945.. w. A; scHuLzE ErAL PROCESS FOR THE TREATMENT OF HYDROCARBONS Filed Jan. 29. 1942 @Een Imis ON/l / ZOFDJOW MOEOJIU mnomno/ /EEE mZON OZCE Patented ct. 9, 1945 ATENT OFFICE PROCESS FOR THE TREATMENT F ROCARBON S Walter A. Schulze and Lloyd C. Morris, Bartlesville, Okla., assignors to Phillips Petroleum Company, a corporation of Delaware Application January 29, 1942, Serial No. 428,773

s claims. (ci. 26o- 6815) This invention relates to the puriiication of hydrocarbons, and more particularly to the selective removal and recovery of specic hydrocarbons from hydrocarbon mixtures by the formation and subsequent decomposition of metal using substantially pure substances, an important problem is presented in the separation of the accompanying hydrocarbons to `produce usable concentrates of the diolelns.

It is known that various materials, especially salts of the monovalent heavy metals of groups I and II of the periodic table, can combine with unsaturated hydrocarbons toform complex salts.

A number of processes have been devised, .using this fact as a basis oi' operation, to separate and recover dioleflns with varying success, depending on the conditions specied for the utilization of these metal salts and on the process refinements designed to overcome 'the non-specificity of the reagents. The product from some of these processes is of insuflicient purity to permit final processing with satisfactory efficiency, thus requiring further purification or providing a product of inferior quality and consequently lowered value.

Since the reaction of the above-mentioned metal salt reagents is not specific for di'olens such as the butadiene hydrocarbons, the utilization of said reagents ln the purification of diolellns'ordinarlly depends on a preferential rate of reaction and/or the formation of a hydrocarboninsoluble metal salt-cliolefin complex. Thus, a

preferred reagent comprises cuprous halides such as the chloride or bromide which produce a solid diolenaddition compound which may be separated under proper conditions from a hydrocarbon mixture and later treated to release and recover the diolen.

, When the cuprous halide reagent is utilized in the form of an aqueous solution,the diolen complex isl formed as a solid precipitate, while the other hydrocarbons may pass unreacted through the contacting zone or may form metal salt comy plexes and be retained in solution'in the aqueous phase. In order to obtain a substantially pure diolefin concentrate it is then necessary to separate thesolid diolefln complex from the aqueous phase and the hydrocarbon phase prior to recovering the diolefin.

Similarly, when solid-type metal salt reagents are used with either liquid or gaseous hydrocarbon mixtures, the diolen addition complex is retained on the reagent surfaces, but the reagent body must be effectively freed of adsorbed and/or condensed non-diolenic hydrocarbons prior to treatment to liberate and recover the diolens. In either case the method of treating the diole- Vfin addition complex to substantially completely remove adsorbed, entrained or occluded extraneous hydrocarbons must be conducted under conditions of temperature and pressure and with reagents which do not induce the decomposition of the diolen-metal salt complex.

In processes for the separation of butadiene from gaseous C4 hydrocarbon mixtures with cuprous halide solutions, it has been suggested that the solid butadiene complex be precipitated from the reaction mixture, and that the solid material and the aqueous solution be heated either toi gether or separately to temperatures which cause evolution of dissolved or chemically combined olens and other extraneous hydrocarbon gases without causing decomposition of the butadiene complex. Such a procedure, however, is not equally applicable to other diolens due to the lower decomposition temperatures of the corresponding diolefin-cuprous halide complexes, and to the higher boiling points of the extraneous hydrocarbons.v For example, to separate the C5 diolens, isoprene and piperylenes, in treating C5 hydrocarbon mixtures, temperatures which cause vaporization and evolution of pentanes and pentenes likewise cause liberation of the chemically combined isoprene and piperylenes.

An object of this invention is to improve the purity of hydrocarbons segregatedl through the formation of decomposable complex addition compounds. Another object is the segregation of dioleflns from hydrocarbon mixtures ln which they occur. Another object is to provide a method for obtaining the dioleiins in substantially Dure state as apart of the separation-process. Still another object'is to disclose a process Wherein low-boiling aliphatic `dioleiins, particularly. those which are normally liquid, are substantially completely separated from hydrocarbons having similar volatility .through the use of metal salt reagents and particularly oi cuprous halide reagents.

According to the process of this invention, a hydrocarbon liquid containing diolens may be contacted with a solution of a cuprous halide, for example, cuprous chloride, whereby the dioleiins form a. complex salt withI the cuprous chloride. The complex, being substantially insoluble in either phase of the mixture, settles out or may be separated in any other suitable fashion. The .precipitated complex is then washed with a parainic hydrocarbon liquid of substantially dilerent boiling point from the dioleiln, and incapable of dissolving or reacting with the complex or any components of the mixture. chloride solution and adsorbed or occluded extraneous hydrocarbons remaining from the original hydrocarbon mixture are substantially completely removed. The washed complex is then decomposed by heating, the dioleiln is recovered, and may be distilled if necessary to remove any amounts of the washing agent which may have been evolved therewith. y

A speciilc arrangement of the steps of this process is indicated diagrammatically in the accompanying drawing. The diolen-containing stream enters the system by line I, passing to the mixing zone 2, wherein it is contacted with an aqueous cuprous chloride solution entering by line 9. The intimate mixture of hydrocarbon and aqueous solution passes by line 3 to separating zone 4, wherein the liquid phases are separated, e

and the hydrocarbon liquid is allowed to overflow at the top. Theaqueous phase, carrying the precipitate of diolen-metal salt complex, passes by line E to separation and/or ltration zone 1, whence the aqueous phase, containing the metal salt in solution, returns by line 9 to contact additional amounts of diolefln-containing feed. Periodically, the ilow into unit A1 is discontinued, and the solid complex is transferred to zone I along line 8, which may represent a screw conveyer, or a similar transporting system for moving the substantially solid material. In zone III,

the complex is washed thoroughly with the wash liquid, entering by line II after cooling in cooler I5, and leaving the zone I0 by line I2. When the precipitate has been contacted suiliciently, the ilow of wash liquid is stopped. A heating By this means, both entrained cuprous 20 to make up for losses of cuprous chloride to the hydrocarbons.

In the foregoing description, it is implied that the process operates batchwise, but this is employed merely for simplifying the explanation since two or more units corresponding to units 'I and I0 may be provided so that operation may be continuous. Therefore, it will be understood that zone 1 and zone II) may represent a. number of such zones, depending on the size and other requirements of the individual installation. Furthermore, the complex may be continuously separated, washed,f and decomposed in a continuous flow system by methods well known to those skilled in the art of material handling.

While the process of this invention is broadly applicable to the separation cf hydrocarbons which form insoluble complexes with inorganic salts such as cuprous chloride, it is especially applicable to diolefins containing live or more carbon atoms, such as isoprene, plperylene and the like. We have found that the cuprous chloride complexes of these and related dioleiins decompose measurably at the temperatures required to vaporize the` non-dioleiinio hydrocarbons of similar boiling point, even when sub-atmospheric pressures are employed.

By the present invention, such losses are avoided, since a wash liquid is used to remove the extraneous unreacted hydrocarbon liquids from theprecipitated diolen cuprous chloride complex without employing conditions causing decomposition of the complex.

medium is passed by lin'e I3 into unit IIl, which is equipped to provide indirect heating to the precipitated complex. The heating medium leaves unit Ill by line Il. 'I'he complex is decomposed by the elevated temperature and the diolen passes out by line I6 to fractionator I1 in which the dioleilnmay be separated from any remaining wash liquid. If the wash liquid is more volatile than the diolen, it will pass overhead by line I8, with the diolen being recovered by line I9. However, if the wash liquid is less volatile than the diolefin, the latter will pass overhead by line I8, and the wash liquid by line I9. After all the diolei'ln has been recovered from the complex, the cuprous chloride may be removed from or dissolved outfrom zone I0 to prepare fresh solution. Cuprous chloride'may also be recovered from the treated hydrocarbons ln line 5 if desired by vapox'lzation or chemical treatment. Fresh cuprous chloride in the formof solid or in the form of a concentrated solu- The liquid washing agent which is a particular feature of this invention is a material chosen in accordance with the requirements for its specie function. Suitable liquids include paramnic hydrocarbons in relatively pure form, or in narrow boiling range mixtures with boiling points substantially different from the boiling points of the dioleilns being purified. Aliphatic hydrocarbons of selected boiling ranges are preferred for many applications, although other liquids may be used such as cycloparaiins, aromatics and the like whose properties conform to the following' specifications. 1

I'hese Washing agents are preferably solvents for hydrocarbons, possess substantially no solvent capacity for the complex, and are unreactive toward uncombined reagent which may be present along with said complex prior to decomposition or present alone during and/or subsequent to the decomposition of said complexes. Further, the washing agents are chosen on the basis of their boiling points which are materially higher or lower than the boiling points of the diolens being. puriiled in order that the final separation of washing agents and diolefins.- if necessary, may be easily accomplished by differences ln volatility. As examples of the selection of washing agents. normal butane is satisfactory for the purication of the cuprous chloride complex of Cs dioleflns, and C1 or Ca paralns or mixtures thereof are suitable examples of higher boiling liquids for the same purpose. Precautions are observed to select washing liquids which do not form objectionable constant-boiling azeotropes with the dl- .olens since such might cause complications in the ultimate recovery of the diolens, after decomposition o! the metal salt complex.

In the vchoice of washing liquids which arev selection but that the sequence of operations may be somewhat different according to whether the washing liquid is higher or lower-boiling than the diolen. Depending largely upon availability and the relative volatility of the diolen being purified, either type of washing liquid may be used according to the terms of the present invention.

If a lower-boiling wash liquid is used, the liquid remaining after the washing step may frequently be removed from the complex by vaporization at temperatures below the decomposition temperature of thecomplex. This vaporization may sometimes remove the wash liquid sufciently completely so that fractionation of the subsequently desorbed diolen is unnecessary.

'I'he washing treatment of the diolen-metal salt addition compounds by our process is carried out at temperatures below those causing desorption of diolelns, and usually at or slightly above temperatures employed in formingv said addition compounds. Thus, when temperatures of to 50 F. are employed in the reaction between dioleiins and the cuprous halide reagents, the washing of the solid complex may be done at corresponding temperatures, or at higher temperature up to about 90 F. To obtain temperatures in this range, pre-cooling of the washing liquid may be necessary.

Temperatures in the range of 115 to 200 F. are ordinarily preferred although higher or lower temperatures may be employed. In many cases it has been found that decomposition of the complex is very slow at temperatures lower than about115 F. so that operation below this temperature level is not ordinarily practiced. Heat- Pressures in the washing operation are ordinarily low superatmosphericpressures sufllcient to maintain flow of the liquid and depending to a certain extent on the temperature and on the boiling point of the washing liquid. Thus, when employing butane or propane at atmospheric temperatures, sucient pressure is provided to maintain liquid phase. With higher-boiling materials, high pressures in excess of those neces-- sary to carry out the washing step by forcing the washing liquid through the bed or layer of soliddiolen complex are usually unnecessary.

The washing liquid may flow through the solid diolen complex or be mixed therewith in any desired manner which produces satisfactory removal of contaminating materials. We may utilize the vessel or filter means used to separate the complex from the reagent solution as a conf tainer for the complex and merely pass the wash liquid therethrough at suitable ow rates and in either upward or downward ow. The flow rate is adjusted to provide satisfactory washing without using excessive volumes of the liquid. Ordinarily from two to ten volumes of wash liquid per ing to temperatures above about200 F. to promote the decomposition reaction may be unsatisfactory and result in excessive consumption of heat and loss of diolefln through polymerization.

While the diolefin leaving the decomposition zone is fairly pure, there is usually a small amount of the washing agent associated therewith. Where propane or butane have been used forA washing, the diolefn may be freed of the washing agent merely by vaporization of the `remaining traces of same. With other solvents, the diol'en may be finally purified by distillation to separate the last traces of the washing agent. This operation is conventional and is easily accomplished since the washing agent has a markedly different boiling point from the diolen. The-diolen may be recovered overhead or at the bottom of the distillation unit depending upon whether a higheror a lower-boiling washing agent has been employed. Following the distillation the diolefin is available in a very highly purified state and substantially undiminished in amount from that entering the treating process. v

The following examples will show applications of this invention. Since, however, many modifications i'nay be made in details of this process wholly within the scope of the invention, no limitation is to be implied by the terms of the exemplary operations.

volume of complex produce adequate removalof contaminants, although more extensive washing may be required. Also, such devices as batch washing may be -employed wherein one batch of liquid is. passed through the solid material and drained or forced out before fresh wash liquid is admitted. These and other modications of the process will be obvious in the light of the foregoing disclosure.

It will be desirable in many cases to provide Ameans for reconditioning the wash liquid to remove hydrocarbons washed from the dioleflnmetal salt complex and., to permit recirculation of the liquid. Such reconditioning may be accomplished by conventionalI means such as redistillation. Aqueous and/or solid material entrained in the wash liquid may be settled out by gravity or removed by other means such as liltration or the like.

In decomposing the diolen complex it is generally our practice to supply the necessary heat to produce desorption temperatures indirectly to avoid contamination of the desorbed diolen.

Example I A charge stock containing 64 volume per cent of isoprene and the balance normal and isopentane, pentene-l and pentene-2 was treated'with a saturated solution of cuprous chloride and ammonium chloride at 35-40" F. The complex formed precipitated out and was removed by :fil tering. The precipitate was then washed at about 50 F. with three portions of liquid butane, each amounting to twice the volume of the solid precipitate. After the last washing, residual butane was removed by vaporization. The decomposition of the complex was then carried out, and the last traces of the butane vaporized from' the condensed diolefin. The product was 99 per cent isoprene, boiling between 93.5 and 94.5 F.,at at- .tical conditions but without the butane wash the product contained only 82 volume per cent isoprene along with 18 per cent pentenes and pen. tanes.

.Example Il' A mixture of hydrocarbons containing 55 volume .per centof isoprene and piperylenes anda per cent of pentanes and pentenes was treated with a cuprous chloride solution at 35 F., and the precipitated complex was removed in a filter. The precipitate was Washed at about 60 F. with two portions of a washing agent, each of which contained about one and one-half times the volume of the precipitate. The washing agent was a parafnic hydrocarbon liquid comprising heptanes and boiling between 180 and 190 F. When substantially all the Wash liquid had drained away, heat was' applied and the mixed complexes were decomposed. The desorbed prod- Example III A C4 hydrocarbon mixture containing 22 per cent butadiene, '74 per cent butenes and the balance normal butane was treated at 45 F. with a cuprous chloride solution, and the. butadiene complex was precipitated and illtered from the aqueous reagent. The solid was washed with several volumes of liquid propane at 50 F. prior to desorption. Residual propane was vaporized while the solid was heated to a desorption temperature of 190 F. and butadiene of over 99 per cent purity was recovered.

The operation herein set forth has been applied particularly to use with solutions of metal salts. f

Solid type reagents, for example, impregnated clays and the like, may also be used under this invention by discontinuing the flow of hydrocar lbon feed, washing the reagent bed carrying the complex, decomposing the complex and distill ing the efuent. It will, therefore, be understood that the use of 'this improved purification prc cedure is n'ot confined to processes employing solution type reagents, but may be applied any process wherein a solid, insoluble complex salt is `formed during the operation.

We claim: 1. In a process of separating aliphatic com jugated diolens from hydrocarbon liquids containing the same and close-boiling non-dioleiinic l hydrocarbons' by contacting said hydrocarbon liquid in the liquid phase with a reagent comprising a salt of a monovalent heavy metal of groups I and II of the periodic system which reacts with aliphatic conjugated diolens to form a hydrocarbon-insoluble solid metal salt-diolen complex and thereby effecting combination of trained non-diolenic hydrocarbons from said l separated complex prior to said desorption step by washing the same with a liquied normally gaseous parainic hydrocarbon which is substantially lower-boiling than the components of said hydrocarbon liquid, and conducting said washing step at a temperature' substantially below that at which said complex decomposes and at a pressure sucientto maintain said normally gaseous parain in liquid phase.

2. In a process of separating aliphatic conjugated Cs diolens from a normally liquid Cs hydrocarbon mixture containing the same and v close-boiling non-diolenic Cs hydrocarbons by contacting said hydrocarbon mixture in the liquid phase with a reagent which is an aqueous soluis butane.

tion of cuprous chloride whereby the C5 diolefln 'content of said mixture selectively combines with said cuprous chloride to form a hydrocarbon-insoluble solid cuprous chloride-diolen complex which is precipitated, separating said precipitated complex, and .desorbing said dioleiln from the separated complex by heating the same to desorption temperature, the improvement which comprises removing substantially all entrained non-diolefmic hydrocarbons from said separated complex prior to said desorption step by washing same with a liquefied normally gaseous parain hydrocarbon which is substantially lower boiling than the components of said hydrocarbon mixture, conducting said washing step at a temperature substantially below that at which said complex decomposesand at a pressure sufficient to maintain said normally gaseous paraffin in liquid phase, and then volatilizing residual normally lgaseous parafiln wash liquid from the complex.

3. The process of claim 2 wherein said paradln WALTER A. SCHULZE. LLOYD C. MORRIS. 

